JPS6041034A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To maintain the sensitivity of a photosensitive material and to reduce fog by using a specified compound as a blocked photographic reagent contained in a photosensitive silver halide emulsion layer of the photosensitive material. CONSTITUTION:A compound represented by formula VII is used as a blocked photographic reagent contained in a photosensitive silver halide emulsion layer of a photosensitive material. Since the pH of the film is 6-7 during storage, even when a compound represented by formula IV or V is partially formed, a reaction by which the compound returns to the original compound represented by formula I takes place preferentially, so the release of A<-> is inhibited. The release of A<-> is remarkably accelerated under alkali conditions during processing because the equilibrium leans toward a compound represented by formula VI. Accordingly, when A<-> is a photographically useful reagent having a timing group, a reaction by which the timing group is cleaved takes place after a reaction by which the compound represented by the formula VI is formed from the compound represented by the formula I , and the photographically useful reagent is released. Thus, the compound represented by the formula VII has high shelf stability and releases rapidly the photographically useful reagent during processing. In the formulae, A is a photographically useful reagent, each of X<1> and X<2> is carbonyl or the like, Z is a group of atoms required to form a 5- - 7-membered ring, and each of R<1>-R<3> is a substituent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive silver halide emulsion layer in which a blocked photographic reagent is combined which releases a photographically useful reagent. Related to photographic materials.

Adding a photographically useful photographic reagent to a photographic reagent in advance to exert its effect is different from adding it to a processing solution and using it. It has the l\ sign. Its characteristics include, for example, that it can be separated under acidic/alkali or oxidizing/reducing conditions, that photographic reagents that cannot withstand long-term storage in a processing bath can be used effectively, and that at the same time, the composition of the processing solution can be studied. 1) It is possible to make adjustments easier, to make it possible to use the necessary photographic reagents at the required timing during processing, or to apply the necessary photographic reagents to the necessary places, i.e., to a certain layer of the multi-sensitivity material. For example, it is possible to make necessary photographic reagents act only on the layer in the vicinity thereof, or to change the structure of photographic reagents as a function of the silver halide phenomenon. however,
If a photographic reagent is added to a photographic light-sensitive material in an active form, it may react with other components in the photographic light-sensitive material during storage before processing or decompose due to the influence of heat, oxygen, etc. The expected performance cannot be achieved during processing. As a method for solving such problems, there is a method of blocking the active groups of a photographic reagent and adding it to a photographic light-sensitive material in a substantially inactive form, that is, as a photographic reagent precursor. When a useful photographic reagent is a dye, blocking the functional groups that affect the spectral absorption of the dye and shifting its spectral absorption toward shorter or longer wavelengths can improve the corresponding photosensitive film. It has the advantage that even if it coexists with the silver halide emulsion layer (f.2) having a small area, a decrease in sensitivity due to the so-called filter effect does not occur. If a useful photographic reagent is an antifoggant or a development inhibitor, by blocking the active groups, it is possible to suppress photosensitivity during storage and the desensitizing effect due to adsorption to silver halide and silver salt formation. By releasing these photographic reagents at the required timing, it is possible to reduce fog without impairing sensitivity, suppress over-phenomenon fog, or stop the phenomenon at a necessary time. There are advantages. When a useful photographic reagent is a developer-assisted developer or a fogging agent, the active agent ↓ or ′ is retained by blocking adsorption groups.

This prevents various photographic effects due to the formation of semiquinone and oxidants due to air oxidation in the silver halide, and prevents fog nucleation during storage by preventing electron injection into silver halide, resulting in stable processing. There are advantages such as Even if the photographic reagent is a whitening accelerator or a bleaching/fixing accelerator,
By blocking these active groups, reactions with other components contained therein can be suppressed during storage, and by removing the blocking groups during processing, the desired performance can be achieved at the required time. It has one advantage.

As mentioned above, the use of precursors for photographic reagents can be an extremely effective means for fully demonstrating the performance of photographic reagents, but on the other hand, these precursors do not meet very strict requirements. There must be. In other words, it is stable under storage conditions, and during processing, the blocking group is unraveled by the necessary tying, and the photoresist 7 is quickly and efficiently released. Must.

Some blocking techniques for photographic reagents are already known. For example, blocking groups such as acyl groups and sulfonyl groups described in the specification of Japanese Patent Publication Akihiro 7-Hirohiro, GOS No. Mono, Special Public Shojt, t-32,727
Same issue! ! -ta t91. No. N5 Yoichi 3≠727, which utilizes a blocking group that releases a photographic reagent through the so-called reverse Michael reaction;
No. 27, Japanese Patent Publication No. 3”7-/3?≠≠ No. j7-/
l from 3! No. r, same, t7-/31. Details of the Hiro θ issue:
one that utilizes a blocking group that releases a photographic reagent upon the production of quinone methide or a quinone methide-like compound through intramolecular ``monotransfer'' described in 2007; and one that utilizes an intramolecular ring-closing reaction described in JP-A No. 43330/1999. or JP-A No. 37-7tjII-1, No. 57-/365
F≠2, same 17-/7? As stated in the specification of the Nihiroλ issue! Techniques that utilize ring cleavage of six-membered or six-membered rings are known as well-known techniques. These known techniques are stable under storage conditions, but the release rate of photographic reagents during processing is too low and p
It requires high alkaline treatment of 1-1/2 or more,
Alternatively, even if the release rate is sufficient with a treatment solution having a pH of 2 to 2, it has the disadvantage that it gradually decomposes under storage conditions, impairing its function as a precursor.

It is therefore an object of the present invention to create a blocked photographic reagent which is completely stable under storage conditions and which releases the reagent at the required timing during processing, especially at pH It is an object of the present invention to provide a blocked and photographic reagent that is compatible with stability under 4kfIi storage and timely release during processing even when processing with a relatively low pil processing solution of 12 to 12.

The object of the present invention is to
In a photographic light-sensitive material containing the combined photosensitive logenated emulsion IVJ, the blocked photographic reagent was achieved by the photographic light-sensitive material represented by the following general formula (I).

General formula (I) (In general formula (I), A represents a photographically useful reagent that may have a timing group. Xl and X2 each represent a carbonyl group, a sulfonyl group, or a sulfinyl group. Z is Represents an atomic group necessary to form a j- to 7-membered ring. Rl, R2 and R3 each represent a substituent, m represents O-λ, n represents O or l,
The sum of m and n is /~3. ) A represents a photographically useful reagent which may have a timing group, and examples of photographically useful reagents include known photographic reagents that tend to bond with heteroatoms, such as mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidine antifoggants and development inhibitors such as mercaptobenzimidazoles, mercaptothiadiazoles, benzotriazoles, and imidazoles; developers such as p-niphenylenediamines, hydroquinones, and p-aminophenols; Auxiliary developers represented by pyrazolidones; fogging agents such as hydrazines and hydrazide; silver rhodanide solvents such as hypo; bleaching accelerators such as aminoalkylthiols; or azo dyes, azomethine dyes, etc. . In addition, as a function of development, 1) a photographic reagent which further has a redox function in which the above photographic reagent is released, such as a coloring material for a color diffusion transfer sensitive material or 1-)
Hydroquinones can also be used as useful photographic reagents. The above-mentioned photographically useful reagents may be bonded via a timing group. ≠-7'II/3j, which releases a photographically useful reagent through an intramolecular ring-closing reaction, British g'Fi Co. No. 072363, JP-A-17-1999
/j4L, a device that releases a photographically useful reagent by intramolecular electron transfer as described in No. 23 Meiflii, etc., JP-A-7
7-/7 Rit≠Those that release photographically useful reagents with the desorption of carbon dioxide gas as described in the specification of No. 2, etc., or those that release formalin as described in the specification of Japanese Patent Application No. 17-20311. Examples include those that release photographically useful reagents upon desorption.

Z represents an atomic group necessary to form a J-membered to 7-membered ring, specifically, an alkylene group, a cycloalkylene group,
Examples include an alkenylene M, y+)-v group, an aralkylene group, an oxyalkylene group, a thioalkylene group, an aminoal[phi]lene group, and a heterocyclyl group.

R1 and R2 may be the same or different (a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an alkyl group, an alkoxy group, an acyl group, a sulfonyl group, a heterocyclic residue, etc.) 1-0 R3 is an alkyl group, an alkenyl group, a cycloalkyl group,
Represents a heterocyclic residue, an aryl group, an aralkyl group, etc.

Among the compounds of the present invention represented by the general formula (I), more preferred compounds are the following general formula (II) and the general formula (Il
l).

General formula (II) 〇General formula (Ill) In general formula (n), A is the same as y' as in general formula (I), XI and X2 each represent a sulfonyl group or a carbonyl group, and R4 is general formula (1) σ month (synonymous with 3. R5 is preferably...a rogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, an amino group, a hydroxy group, a carboxyl group, an alkyloxycarbonyl group, aryloxycarbonyl group,
Represents a carbonamide group, sulfonamide group, ureido group, sulfamoylamino group, oxycarbonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, cyano group, sulfo group, nitro group, etc. n represents O or /, k represents O or ≠, and when k is λ to Hiroshi R
5 may be different groups.

In general formula (1), A has the same meaning as in general formula (I), Xl and X2 each represent a sulfonyl group or a carbonyl group, and R6 has the same meaning as R3 in general formula (I). R7 and R8 may be the same or different, and preferably represent a hydrogen atom, a -.rogen atom, or an alkyl group.

Y is an oxygen atom, a sulfur atom, 11 (* has the same meaning as R6, R10 and R11 represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, etc., and l is / to λ.

When l is 2, R10 and R11 on the λ carbons may be different, or a 2@ bond may be formed between the two carbons. Similarly, in the case of l #”-/, a λ double bond may be formed between R and the carbon atom substituted by R8,
Furthermore, a 7-chloro ring or a hetero ring may be formed between R7, R8, 几10 and R11.

In the general formula (]'[), particularly preferably, X represents a carbonyl group, X2 represents a carbonyl group or a sulfonyl group, and R4 represents a substituted or unsubstituted alkyl group. R5 represents a -.logen atom, a carbonamide group, a sulfonamide group, a ureido group, a carbamoyl group, a sulfamoyl group, or a nitro group, and k represents O-2, preferably O or/. m+' represents 10 to 3, preferably 1 to λ. n represents 0 or l; when n is 00, m preferably represents ko; when n is l, 1n preferably represents l.

In general formula (III), particularly preferably, X and X2 represent a carbonyl group, R6 represents a substituted or unsubstituted alkyl group, Y represents an oxygen atom or an atom, and l
represents / and R7 and R8 represent a hydrogen atom or a substituted or unsubstituted alkyl group.

The reason why the precursor compound of the present invention has excellent storage stability and simultaneously releases a photographically useful reagent during processing is not clear, but it can be considered as follows. first,
Assume that the mechanism of release of photographically useful reagents from the precursor compounds of the present invention is shown as shown in the scheme.

(In the general formula (I), Xl and X2 each represent a carbonyl group, and the same applies to sulfonyl groups.
It can be shown in p. ) (I) (IV) Scheme 1 In scheme 1, the process from (I) to (■) is a reversible reaction, and the pH of the film 1 during storage is
is t ~ 7, so even if some (pieces or (V)) are formed, the reaction that returns to (I) takes priority and the release of 80 is suppressed, but under alkaline conditions during treatment. Then, the equilibrium is (
It is thought that the release of 80 is significantly promoted because it is biased towards Vl).

In the case where 80 is a photographically useful reagent having a timing group, a timing group cleavage reaction is added following the reaction of producing (Vl) from (I) to release the photographically useful reagent.
This seems to be more advantageous in terms of storage stability.

The preferred amount of the compound of the present invention to be added varies depending on the type of the photographically useful reagent, but the antifoggant and development inhibitor is silver 1
lo-8 to 10-1 mol per mole, preferably 10-6 to 10-1 mol for mercapto antifoggants, 10-5 for azole antifoggants such as benzotriazole
~io” mole, developer is 10” per g mole ~1
0 mol, preferably 0, / ~ omole, pyrazolidone co-developers from 10' to 10 mol, preferably 1 o -2 to 3 mol per mol of silver, fogging agent from 1 to 1 mol per mol of silver.
o-2 to 10' mol, preferably io'' to 1O-
5 mol, -, warts, etc. - Silver halogenide solvents are 1o-3 to 10 mol per mol of silver, preferably lo-2 to 1 mol, and bleaching accelerators such as aminoethanethiols are 1o-3 to 10 mol per mol of silver. -5 to o, imol, preferably lo-4 to l0
-2 moles, dyes or color diffusion transfer photographic colorants from lo-3/mol per 7 moles of silver, preferably! ×10
-3 to O0j moles.

Next, specific examples of the precursor of the present invention will be shown, but the present invention is not limited thereto.

11 (131oc[13 CI13) The toughlecaser compound of the present invention represented by the general formula (I) can be easily synthesized, for example, according to the following schemes 1 and -.

fil) (■) (■) (I) (n=0) Scheme/ (■) (X) (Xl) (Ni-suke scheme λ In other words, as shown in Scheme 1, if <n=o, anhydride By heating dehydration condensation of (■) and amine body (■),
After obtaining the imide compound (IX), CI )(n=0) can be obtained.

In addition, when n is l, as shown in scheme λ, after obtaining the diamide form (>1) in the condensation reaction between the diamino form (X) and the anhydride (■), phosgene Alternatively, by using a phosgene dimer to form carbamic acid chloride (XIII), and by substitution reaction with a photographic loading reagent or a photographically useful group having a timing group, (I) (, .

Specific synthesis examples of the precursor compound of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplary Compound (2)> N-7 talluglymine obtained by dehydration reaction of phthalic anhydride and glycine //, 1≠g <o.

M
1 and cooled to 00C. Dicyclohexylcarbodiimide i3. trtg(o.

063) in DMF solution (jOml) was added dropwise.

After dropping, remove the cooling bath, stir at room temperature for 3 hours, and set aside overnight. The reaction mixture is cooled and the urea formed is removed. The furnace solution was poured into water and extracted using a 111-toe filter, and the organic layer was washed with water and then dried over anhydrous Na2SO4. After distilling off the solvent, Nial is added to obtain crude crystals of tyg. ``) When recrystallized from TOETHI/hexane, m, p
/ 7.2°~/Otsu ψ00 lh, jg of the title compound is obtained.

Synthesis Example 2 <Synthesis of Exemplary Compound (6)> Phthaloylglycine//, Al1-. q(θ, 06 mok
) and/, j-diphenyl-λ-hydroxymethyl-3-
Oquinopyrazolidine/l, 02. q (0°6 moles)
and a catalytic amount of gauge methylaminopyridine in DMF, 20
Dissolve in 01rLe and cool. Among them, cyclohekiful carbodiimide i3. t, ty(0,01,it
mole) in DMF solution! Drip Ogo. After the addition is complete, remove the cooling bath and leave at room temperature overnight. The reaction mixture is cooled and the urea produced is taken into account. Pour I3f night into water and extract with darkness: ethi. After the obtained organic layer is completely washed with water, it is dried with anhydrous Na2SO4. After evaporation of the solvent, ether is added to the oil to obtain crude crystals. Vinegar Echi/
When recrystallized with hairsan, the title compound is m, p/76
It is obtained as white crystals of -/7'7°.

Synthesis Example 3 <Synthesis of Exemplary Compound (14)> Synthesis of acetic acid Pyridine-λ,3-dicarboxylic acid anhydride 2jfl(0,
/g mole) and glycine/2. OtsugcO.

g mol in l) and triethylamine/, 7jj (0°0/
l1 mol) total toluene 200 rnl. The mixture is heated to reflux for an hour and the water formed is continuously removed. When hot, the reaction mixture is filtered to remove insoluble matter, and the liquid is cooled to obtain crystals. Recrystallization from ethyl acetate and hexane yields the title compound with m and p/33 to 13j0.

(Pyridine-2,3-dicarboxifimidoyl) 30 fl (0,/hirot mol) of acid and /-hydroxymethyl-
Yo-methyl-benzotriazole, 23°7, j9
(0,/'IA mol) Dissolve the Hiro-dimethylaminopyridine of Catalyst R in DMFIIooml and cool. In it, 3t of dichlorohexylcarbodiimide
,/g of DMF8i'il (/00ml) wor+
After dropping, the cooling bath was heated to room temperature for 21 minutes. The reaction mixture is cooled and the urea formed is filtered off. Pour the furnace solution into water and add chloroform to 1
The organic layer obtained from 111 was washed with water and then dried over anhydrous Na2SO4. After evaporation of the solvent, the obtained crude crystals were
When recrystallized with ethyl/ether, m, p/tata 0~-
The title compound of 2010 is obtained atg.

Synthesis Example 4 Synthesis of Exemplified Compound ae>! -Synthesis of methyl-7-anilinomethylbenzotriazole/-hydroxymethyl-y-methylbenzotriazole j, 01/(0.03 mol) and aniline λ.

Suspend J (0,03) in ethanol and reflux for 1 hour. After heating the solution, cool the furnace liquid to obtain crude crystals. When recrystallized with ethanol, m, pl≠
the law of nature~/! The title compound of -2° is obtained in Hiro0.2I.

Synthesis of Exemplary Compound a0 N-phthaloyl glycine i, 2yll (6,jjXIO
) toyo-methyl-l-anilinomethylbenzotriazole i, sl, I (6, zr×to ) in DMFjOln
Dissolve in l and cool. Synchhexylcarbodiimide 1. Hiroshig<t, ♂×10) in DMF (10ml
). After the dropwise addition is completed, leave at O0C for 5 hours. Filter the generated urea and pour the filtrate into water and extract with acetic acid. The organic layer is washed with water and dried over anhydrous Na2SO4. After distilling off the solvent, the When the compound was separated by 7-lack column polychromatography, the title compound was m, p/-2
≠30 g of white crystals of 7~/3jt are obtained.

The precursors used in the present invention may be used in combination of λ or more types.

Blocked photo test 4 of the present invention ('f Recurser,)
Silver halide photographic light-sensitive materials include silver halide emulsion, agent layer, colorant layer, undercoat layer, protective layer, intermediate layer, filter layer, antihalation layer, receiver (image layer, cover sheet layer, etc.) It may be added to any of the auxiliary layers.

In order to add the precursor used in the present invention to these layers, the precursor may be added as is or in a solvent that does not affect the photographic material, such as water or alcohol, in the coating solution for forming the layer. It can be added by dissolving it at an appropriate concentration. Alternatively, the precursor can be dissolved in a high boiling point organic solvent and/or a low boiling point organic solvent, and added by emulsifying and dispersing the solution in an aqueous solution. Also, Tokukai Akira! /-JYIjtJ issue, same jt/-1 dede l
I2, same evening≠-32312, U.S. Patent Hong, /! 1! the law of nature,
It may be added by impregnating it into a polymer latex by the method described in Japanese Patent No. 363 or the like.

Although the precursor of the present invention may be added at any time during the manufacturing process, it is generally preferable to add it immediately before coating.

The compounds of the present invention can be used, for example, in coupler-type color photographic materials.

A general method for forming a color image from a color photographic light-sensitive material is to convert a silver halide light-sensitive material into an aromatic first photosensitive material in the presence of a color coupler that has the ability to form a dye by reacting with an oxidized form of a developing agent. This is a method of obtaining azomethine or indoaniline dye gold by developing and imaging using a class Aban phenomenon crude drug. This color development method is basically 3
! It was invented by DMannes & L. Godowsky in 1999, and its improvements have been made and are used in the industry worldwide today.

In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, virazolobenzimidazole, or cyanoacetopheno/indacylon coupler is mainly used. are used, and primarily phenolic couplers, such as phenols and naphthol 1-11, are used to form cyano-colored images.

Normally, color photographic materials are made of high-quality materials. The method is roughly divided into an external type method in which the coupler is placed in a Schiller developer solution and an internal type method in which the coupler is placed in each photosensitive layer of the photosensitive material with V' contained therein so as to maintain an independent function. In the latter, the coupler (2) that forms the dye image is added to the silver halide emulsion. It needs to be standardized.

In the internal mold method, the processing process for color photographic materials basically consists of the following three steps.

(1) Color development process (2) Bleaching process (3) Fixing process The bleaching process and the fixing process can be performed simultaneously. That is, it is a bleach-fixing step (so-called Brix), and this step desilveres developed silver and undeveloped silver halide. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process also includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the shelf life of the image. Accompanying. For example, a hardening bath is used to prevent excessive softening of the photosensitive film during processing, a stop bath is used to effectively stop the development reaction, an image stabilization bath is used to stabilize the image, and the backing layer of the support is removed. Kingship, such as the removal of membranes, is mentioned.

Conventionally known methods of adding or dispersing couplers to emulsions and methods of adding them to gelatin/silver halide emulsions or hydrophilic colloids are applicable.

For example, a method of mixing and dispersing a coupler with a high-boiling organic solvent such as dibutyl phthalate, tricresyl phosphate, wax, higher fatty acids and their esters, etc., for example, US Patent No. λ, 30'1. ri No. 32, No. 2,322.0
The method described in No. 27, etc. Another method is to mix and disperse the coupler with a low boiling point organic solvent or water-soluble T4M shavings. A method of dispersing couplers in combination with a high boiling point organic solvent.

For example, U.S. Patent No. 2,207.170, 2°10/
, No. 171, No. 2.9119.360, the coupler itself has a sufficiently low melting point (e.g.
j0C or less), a method of dispersing it alone or in combination with other couplers such as colored couplers or uncolored couplers. For example, the description in German Patent No. 1/≠3゜707 is applicable.

Dispersion aids include commonly used anionic surfactants (e.g. sodium alkylbenzene sulfonate,
Sodium di-octyl sulfosuccinate, sodium dodecyl sulfate, sodium alkylnaphthalene sulfonate, Fischer type couplers, etc.) Amphoteric surfactants (e.g. N-tetradecyl/N-N dipolyethylene alpha betaine, etc.) and nonionic surfactants (For example, sorbitan, monolaurate, etc.) are used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color-forming coupler that forms color through oxidative coupling with an aromatic 7th class amine developer (for example, a phenylene diamine derivative or an amine phenol derivative) during color development processing. It may also contain a vine compound. For example, magenta couplers include terpyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, and open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, piparoylacetanilides, etc.). ), etc., and 7 uncouplers include naphthol couplers, phenol couplers, etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either ≠ equivalent or di-equivalent to the silver ion.

It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor along with a phenomenon (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

When applying color diffusion transfer photography VC to the photographic element of the present invention, peeling (peel anomite) or the method described in Japanese Patent Publications Sho≠A-/Otsu No. 3JT, Shiguf, No.-33427, JP-A No. 10-130110, and British Patent/, 330. Yoλ
An integrated type as described in the ≠ issue, JP-A-7-/-31! It is possible to adopt a film unit configuration that does not require peeling of 14 feet as described in the issue.

The compounds of the present invention can also be used in black-and-white photosensitive materials. Examples of black-and-white photosensitive materials include X-ray film for direct mounting, black-and-white film for general printing, lithography film, and scanner film.

Other constitutions of the silver halide photographic material of the present invention, such as a method for producing a silver halide emulsion, halogen composition, crystal habit, grain size, chemical sensitizer, antifoggant, stabilizer, surfactant, gelatin There are no particular restrictions on curing agents, hydrophilic colloid binders, matting agents, dyes, sensitizing dyes, anti-fading agents, anti-color mixing agents, polymer latex, brighteners, antistatic agents, etc. For example, Re5earchD
isclosure / Volume 76 1), 2.2-113
You can refer to the description in / (December /27r).

Further, there are no particular limitations on the exposure method, the rendering method, etc. of the silver halide photographic material of the present invention, and for example, the above (R
esearch Disclosure) Part 2r~30
Any of the known methods and known treatment liquids as described on page 1 can be applied. Depending on the purpose, this photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing). Processing temperature is normal/
The temperature is selected between 1r0C and jOoC, but the temperature may be lower than /f'c or higher than jo0c.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. /-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p
-aminophenol), etc. can be used alone or in combination. The developing solution generally contains a known preservation agent, alkaline agent, H buffering agent, anti-fogging agent, etc., and, if necessary, a solubilizing agent, a color toning agent, an image accelerator,
It may also contain a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like.

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" phenomenon processing is for photographic reproduction of line images or halftone images using dihydroxybenzenes as a developing agent and under low sulfite ion concentration. This refers to a developing process that causes the developing process to be carried out contagiously.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (for example, ≠-amino-N, N-diethylaniline, 3-methyl-Hiro-amino-N, N-,2-ethylaniline, Hiro-ami/ -N-
Lf-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-β-hydroxyethylaniline, 3-methyl-≠-aminoh-ethyl-N
-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, Photogr by L, F, A, Mason
aphicProcessing Chemistry
(Focal Press, 1247) 22≦~
λλ page, U.S. Patent No. 2, No. 3,0/j, U.S. Patent No. 2,39
2.36, JP-A-Kokai Akihiro Za-233, etc. may be used.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process or separately. As bleaching agents, compounds of polyvalent metals such as iron (lit), cobalt (GV), chromium (Vl), copper (l[), etc., peracids, quinones, nitroso compounds, etc. are used. The present invention will be further explained below with reference to Examples.

Precursor compound 3. Dissolve tXlo moles in acetonitrile with
on buffer-zorul was also added to the mixture. (The measured pH was adjusted in advance to /θ·0 by the pH of the buffer solution.) After a certain period of time, a certain amount of the reaction solution was taken, and the pH was adjusted to 2j with acetic acid to stop the reaction. Quantifying photographically useful reagents released by heavy-speed liquid chromatography,
From the pseudo-order reaction rate constant 1('), the half-life t/ which is the time required for half of the precursor to react
/2=0, calculated from the formula 4ri3/ni'. Similarly, comparative compounds 1-A and /-13 were also compared with the precursor compound of the present invention using 1//λ, and are shown in Table 2.

Table 7 Determination of release rates of photographically useful reagents (acetonitrile/buffer=///.

pH=to,o,,2J-'C) Compound/i6'(sec)t//-2('5ec
)4 Exemplary compound (2),! , lo x to 3
Jo.

4 ff ((3) , 2.jri×10 2t703 # ([4) 4Z-/7X#) #4 Comparative compound/
-A 1. ! 3×10 Hiroj30〃 7f-'B7 Morihiro×l0-5 Ta310 comparison compound/-A and/-33
The structure is as follows: /-A From Table 7, it can be seen that the release rate of the benzotriazole antifoggant and phenidone compound of the precursor compound of the present invention is one bit higher than that of the existing precursor compound. Furthermore, it has been revealed from Examples 2 and 3 below that the storage stability in the coating film is excellent, and this fact suggests the multi-step cleavage mechanism mentioned above. Conceivable.

Example 2 To evaluate the effectiveness of all the antifoggant + h agent precursors of the present invention, the compounds of the present invention and their control compounds, the subbing layer was coated with a cellulose triacetate film support of Ct,'d. An emulsion layer containing the antifoggants shown in Table 1 and the blocked antifoggant of the present invention dissolved and emulsified in tricresyl phosphate together with a coupler (Cp-/) was added on the body. Samples A-F were prepared by coating. The amount of each substance applied is fJ
It is shown in parentheses as /m2 or mol/m2.

(1) Negative silver iodobromide emulsion, grain size /, Il-μ (silver /
, 6X10 "moA'/m2) Mai/Tacoupler C
p-/ (/・3×10-3m01!/m2) force 'l') inhibitor or 7C is its precursor f- (specified in Table 2). Gelatin (/, 30 i/m2, λ, Hiro-dichloro-2-hydroxy-S-) riazine sodium salt (0.0/m2) These films were left under conditions of HirooOc1 relative humidity of 70% for 71 hours. After that, imagewise exposure for sensitometry was applied, and the next color phenomenon was performed.

Color 3Jl image processing process Time Temperature l Color development 3'/j// 3toC2f vote White
t' 3oti 3 Water washing λ' Hiro Fixation Hiro' 3f oc Ma Water washing ll t Stability ll Here, the compositions of each processing solution in the color development processing step are as follows.

Color developer water goome ≠-(N-ethyl-N~hydroxyethyl]amino-λ-methylaniline sulfate Jj) Sodium sulfite j,! / Hydroxylamine sulfate 2.57 Potassium carbonate 30g Potassium hydrogen carbonate i,,2y Potassium bromide /,,2￥ Sodium chloride. 0.2g sodium nitrilotriacetate /, add 2jj water /
1 (1] HIO0/) Bleach solution water toomt Ferric ammonium salt of ethylenediaminetetraacetic acid / 009 Disodium ethylenediaminetetraacetic acid iog Potassium bromide / 10g Butyric acid iog Add water /1 (pHA, θ) Fixer solution water 1ooml Ammonium thiosulfate / jOji Sodium sulfite 10g Sodium hydrogen oxide λ,!!! Add water 1
l (pH &, θ) Stable liquid water room Formalin (37%)! Godreiwell 3d Water was added to /l and the photographic properties are shown in Table 2.

From Table C, it can be seen that in BD using the compound of the present invention, fog is reduced with almost no decrease in sensitivity.

Therefore, it can be said that the precursor compound of the present invention stably exists in the film and releases an antifoggant during processing, thereby specifically reducing fog without desensitizing the film.

The antifoggants and couplers used for comparison were as follows 4).

1 Comparative Compound λ-A Comparative Compound 2-13 () Example 3 To evaluate the effectiveness of the (co-developer) precursor in the present invention, the compounds of the present invention and their control (comparative) compounds, the undercoat 1r1 The (co-developing agents) shown in Table 2 and their precursors were added to the coupler (C
Sample G-
K was prepared. The coating solution for each substance is l/m2 or mO
It is shown in parentheses as l/m2.

(1) Emulsion layer Negative silver iodobromide emulsion, grain size 1, vμ (silver 4 x 10" mol/m) magenta coupler Cp'-/ (i, 33 x 10 mol/rn) (auxiliary developer)
or its precursor (/, 33X10 mol/
m) Gelatin (,2,jOji/m) (2) Hosun layer gelatin (/,30zo/m) Ko, Hiro-dichloro-2-hydroxy-8-triazine sodium salt (o,or,q7m) These films After being left for 7 hours under conditions of ≠o 'C and relative humidity of 7 (1)%, imagewise exposure for sensitometry was applied and color development processing similar to that in Example 2 was performed.

The obtained photographic properties are shown in Table 3.

As is clear from Table 3, in the samples to which the auxiliary developer was added as is, fog increased and desensitization occurred, but in Samples H and I using the compounds of the present invention, fog did not increase at all. Sensitize with

The auxiliary developer J-A, 3-13 used here is as follows.

Patent applicant Fuji Photo Film Co., Ltd. Procedural Amendment 16 Case Display Showa! Patent application No. 1≠t9io No. 2,
Title of the invention: Silver halide photographic light-sensitive material 3; Relationship with the person making the amendment: Patent applicant name (520): Fuji Photo Film Co., Ltd. 4; Subject of the amendment: "Detailed description of the invention" column 5 of the specification; The statement in the "Detailed Description of the Invention" section of the Description of Contents of the Amendment is amended as follows.

l) Page 3, line 3 After "Developer" 「・」 Insert.

, 2) 1st/page bottom jth line r-R9N-J [-N- R] and correction 1-ru.

3) Page 11, bottom j line “R10 iLJ "R.J.O. ■ -((lt- 11 , I and correct it.

4.Replace the second part of the text with the full text of the rooster in Attachment-1.

27th page io ~ // line "Phosgene dimer" "Thiophosgene" and correct it.

B) Page 27, line 13 rX': Delete CU, J.

7) Page 27, bottom row "N-phthaluglymine" [N-phthaloylglycine J and correct it.

d) No. 2, page 2g, line 2 “≠-dimethylaminopylidene] "μm dimethylaminopyridine" and correct it.

ri) No.≠Page 2, bottom 5th line After “half-life” "all" Jri alone.

Attachment-7 1 (■) (X) 1 (XI) (Xll) scheme l

Claims (1)

[Scope of Claims] In a photographic light-sensitive material containing a light-sensitive silver halide emulsion layer in which a blocked photographic reagent is combined, the blocked photographic reagent is represented by the following general formula (I). Featured silver halide photography! ,~light materials. In the general formula (1) (general formula CI), A represents a photographically useful reagent that may have a timing group. Xl and X2 each represent carbonyl, a sulfonyl group or a sulfinyl group. Z represents the atomic group necessary to form a 7-membered ring. R1, R2 and R3 each represent a substituent, m represents O-2, n represents O or /,
The sum of m and n is /~3. )